Optically active indane polymers

ABSTRACT

Optically active polycarbonate, polyester, and polyurethane polymers prepared from monomers containing optically pure indane moieties are disclosed. The chiral indane polymers are of high molecular weight and exhibit high optical rotations. In addition, the optically active polymers are useful in the fabrication of optoelectronics devices and as polarizing coatings or filters or as polarized lenses.

The following invention was made with Government support under contractnumber F33615-95-C-5432 awarded by the United States Air Force. TheGovernment has certain rights in this invention.

FIELD OF THE INVENTION

The present invention relates to chiral polymers derived from indanebisphenols, and more particularly to high molecular weight opticallyactive linear indane polycarbonate, polyester, and polyurethanepolymers.

BACKGROUND OF THE INVENTION

Chiral materials exhibiting no center of symmetry are isotropicbirefringent materials having a "handed" molecular structure. Thishandedness makes them optically active and capable of rotating a planeof polarized light transmitted through them. Polarizing coatings andfilters comprise birefringent materials capable of transforming lightinto polarized light. Thus, chiral materials may be used as polarizersin the fabrication of plane polarized lenses and polarizing coatings andfilters.

Recently, Pelet and Engheta in IEEE Transactions on Antennas andPropagation 38, 90-98 (1990) have suggested the use of optically activematerials in guided-wave structures to produce chiral waveguides. Achiral waveguide, also known as a chirowaveguide, comprises acylindrical waveguide or parallel conducting plates filled with ahomogeneous isotropic chiral material. Applications for chiralwaveguides include integrated optical devices, telecommunicationselectronics systems, printed-circuit elements, and optoelectronicsdevices.

Organic polymers are known to be compatible with semiconductorelectronics technology, can withstand high temperatures duringprocessing, and have a large capacity for engineered properties. Inaddition, it is well-known that high molecular weight polycarbonates areexcellent materials for optical applications because of their inherenttoughness, durability, resistance to heat and cold, and clarity. Themost familiar linear polycarbonates arc homopolymers derived from2,2-bis(4-hydroxyphenyl)propane, commonly known as bisphenol-A (alsoreferred to herein as "BPA"). Polycarbonates derived from BPA areoptical quality plastics that can be injection molded to form opticalmaterials such as lenses, substrates for optical storage media includingcompact disks, and automotive tail lights, for example.

Less familiar polycarbonates are those reported by Wimberger Friedl etal. in U.S. Pat. No. 5,424,389 and European Patent Application 0621297A2and disclosed by Faler et al. in U.S. Pat. No. 4,950,731. Thesepolycarbonates comprise random copolycarbonates of BPA and6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane (also referredto herein as "SBI"), which also exhibit the requisite propertiesnecessary for such optical applications. Random copolycarbonatescomprising BPA and SBI are also reported by K. C. Stueben in J. PolySci., Part A, 3, 3209-17 (1965). Copending commonly assignedapplications, U.S. Ser. Nos. 08/920,931 and 08/798,756 (U.S. Pat. No.5,703,197), disclose alternating linear polycarbonates derived fromspirobiindanols and dihydroxyaromatic compounds, homopolycarbonatesderived from indanols, and random and alternating polycarbonates derivedfrom indanols and biphenols and bisphenols. The aforementionedpolycarbonates are also transparent and exhibit excellent thermal andmechanical properties.

Poly(aryl)esters, or polyarylates, are high molecular weight aromaticpolyesters derived from aromatic dicarboxylic acids and phenols.Polyarylates are known to exhibit mechanical and thermal propertiessimilar to those of polycarbonates. In particular, they are thermallystable at high temperatures, resilient, tough, durable, hydrolyticallyresistant, transparent, and exhibit excellent processability. The mostcommon polyarylates are those prepared by the reaction of isophthaloyland terephthaloyl chlorides with BPA.

J. C. Wilson discloses polyesters containing derivatives of racemicindane compounds in J. Polymer Science: Polymer Chemistry Ed. 13,749-754 (1975). The racemic indane polyesters were found to exhibit highglass transition temperatures ranging from 244° C. to 272° C. Inaddition, U.S. Pat. No. 3,634,089 to Hamb discloses polyesters preparedfrom racemic indane bisphenol compounds and specific bisphenols, such asBPA. The polymers exhibited a weight average molecular weight of atleast 30 kg/mole, a glass transition temperature of at least 200° C.,desirable thermal properties, and good optical clarity.

Polyurethane polymers are high molecular weight thermoplastic polymersuseful in a variety of forms, such as fibers, coatings, elastomers, andfoams. As coatings, the polyurethanes exhibit excellent hardness,flexibility, abrasion and hydrolytic resistance, and adhesion. Inaddition, they are tough, durable, and thermally stable at hightemperatures. Polyurethanes are often used as wire coatings inelectrical applications. The Stueben reference mentioned above disclosespolyurethane polymers prepared from racemic SBI.

In general, most applications of synthetic polymers require good thermalstability to withstand high temperature processing (>150° C.), but donot require optical activity. However, for use in the formation ofpolarizing coatings, lenses, or filters and for utility as chiralwaveguides in optoelectronics devices, birefringent materials havingpolarizing properties must be employed. Due to the low birefringence ofthe achiral prior art polycarbonate, polyester, and polyurethanepolymers mentioned above, they are not useful in such applications.

A need therefore exists for optically active organic polymers thatretain the same advantageous properties associated with high molecularweight polycarbonates, polyesters, and polyurethanes. In particular,such chiral polymers should have excellent processability and highmolecular weight, and should be durable, tough, thermally stable andwater resistant. The novel chiral indane polycarbonate, polyester, andpolyurethane polymers of the present invention meet the above need.

SUMMARY OF THE INVENTION

The present invention is based on the discovery that compoundscontaining optically pure indane moieties can be polymerized to form awide variety of unique optically active polymers. The novel chiralpolymers of the present invention exhibit similar properties to thoseassociated with the high molecular weight polymers mentioned above.However, unlike known polycarbonates, polyurethanes, and polyesterpolymers, the present optically active linear polymers have additionalapplications, such as in the field of optoelectronics in the fabricationof chiral waveguides. In addition, the present chiral polymers can beused as polarizing lenses, coatings, and/or filters. The presentpolymers are characterized by their high optical rotations and highmolecular weights, typically between about 10 kg/mole and 500 kg/mole.

More particularly, the novel optically active linear polymers of thepresent invention are polymerized from monomers containing opticallypure indane moieties of formulas (IA) and/or (IB) below, also referredto herein as "indanes". The chiral indane monomers are typically derivedfrom the enantiomers of5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-tri(R²)indanes, wherein R² isdefined below. These dihydroxy compounds are referred to herein as"indanols" or "indane bisphenols". The chiral indanes may be substitutedor unsubstituted.

The optically active linear indane polymers of the present inventioncomprise structural units having formula (IA) and formula (IB) ##STR1##and structural units selected from the group having formulas (II)-(III)or (VI)-(XII) ##STR2## wherein m is the mole fraction of structuralunits (IA) in the polymers, and n is the mole fraction of structuralunits (IB). The numerical value of m and n is each independently from 0to 1.0, and the numerical value of m differs from the numerical value ofn. The sum of m and n is less than or equal to 1.0.

Structural moiety (II) is typically derived from a racemic substitutedor unsubstituted indane bisphenol compound. The spirobiindane moiety offormula (III) is generally derived from a6,6'-dihydroxy-3,3,3',3'-tetra(R²) spirobiindane, which may besubstituted or unsubstituted.

In structural units (VI), x is 0 when (VI) is a moiety derived from asubstituted or unsubstituted bisphenol. Alternatively, x is 1 when (VI)is derived from a substituted or unsubstituted bisphenol, such asbisphenol A, wherein each R² is methyl, or such as hexafluorobisphenolA, wherein each R² is trifluoromethyl. In structural units (XI), y is 1to 20. Structural units (IX)-(XI) are derived from corresponding diacidhalides. When structural units having formula (IX), (X), (XI), or (XII),which is derived from a diisocyanate compound, are included in thepolymer, then each of the structural units is separated by at least onestructural unit of formula (IA) or (IB).

The mole fractions of structures (IX) and (X) are 1-f(m+n) and 1-f'(m+n), respectively, wherein f and f' are each 1 except if the sum of mand n is about 0.5, then f and f' may each independently have a valuegreater than 1 but less than 2, and both formulas (IX) and (X) areselected as structural units in the polymer.

Each R¹ and each R² in the structural formulas above is independentlyhydrogen, deuterium, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl,alkoxyaryl, alkylaryl, arylalkyl, alkoxy, alkoxyalkyl, aryloxyalkyl,haloalkyl, haloaryl, nitro, halogen, cyano, hydroxy, or deuteratedequivalents thereof. Preferably, each R¹ is hydrogen or deuterium, andeach R² is methyl, trideuteromethyl, or trifluoromethyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to novel optically active linear polymerscontaining optically pure indane moieties of formulas (IA) and/or (IB)above. The chiral polymers include indane polycarbonates, polyurethanes,and polyesters. More particularly, the polymers include optically activehomopolycarbonates comprising structural units (IA) or (IB) derived fromthe enantiomers of corresponding chiral indanols and also includeoptically active random copolycarbonates comprising both structural units (IA) and (IB) in differing molar amounts. In addition, the opticallyactive polymers include alternating linear copolycarbonates,copolyesters, and copolyurethanes in which structural units (IA) or (IB)alternate with structural units chosen from formulas (II)-(III) or(VI)-(XII). The alternating copolymers may contain both optically activeunits (IA) and (IB) in differing molar amounts, wherein each selectedstructural unit (II)-(III) or (VI)-(XII) alternates with a structuralunit of (IA) or (IB), but otherwise, the placement of each (IA) and (IB)structure in the chain is completely random. Also included within thepresent invention are random linear copolycarbonates in whichenantiomeric structural units (IA) and/or (IB) are randomly dispersedwith structural units chosen from structures (II), (III), (VI), (VII),or (VIII) throughout the polymeric chain. The present polymers alsoinclude optically active indane polyester (polyarylate) polymers whereinstructural units (IA-IX) and (IA-X) or (IB-IX) and (IB-X) are randomlydistributed throughout the polymer. Also included within the presentinvention are polymers containing chiral indane polyester oligomersrandomly dispersed with optically active indane polycarbonate monomers.Similarly, polymers containing chiral indane polyurethane blocksrandomly dispersed in the chain with optically active indanepolycarbonate monomers are disclosed.

Each R¹ and R² substituent of chiral indane structural moieties (IA) and(IB), of racemic moieties (II) and (III), and of the achiral moieties(VI)-(XII) is independently hydrogen, deuterium, alkyl, cycloalkyl,alkenyl, cycloalkenyl, aryl, alkoxyaryl, alkylaryl, arylalkyl, alkoxy,alkoxyalkyl, aryloxyalkyl, haloalkyl, haloaryl, nitro, halogen, cyano,hydroxy, or deuterated equivalents thereof. Illustrative useful R¹ andR² substituents are hydrogen, alkyl such as methyl, ethyl, butyl,pentyl, octyl, nonyl, tert-butyl, neopentyl, isopropyl, sec-butyl,dodecyl, and the like; aryl such as phenyl; cycloalkyl such ascyclohexyl, cyclooctyl, cycloheptyl, cyclopentyl, and the like;alkoxyalkyl and aryloxyalkyl such as phenoxymethylene, phenoxyethylene,methoxymethylene, ethoxymethylene, methoxyethylene, butoxymethylene,propoxyethylene, and the like; arylalkyl such as phenylethyl,phenylpropyl, benzyl, and the like; and substituted alkyl and arylgroups such as cyanomethyl, 3-chloropropyl, 3,4-dichlorophenyl,4-chloro-3-cyanophenyl, chloromethyl, dichloromethyl, trichloromethyl,fluoromethyl, difluoromethyl, trifluoromethyl, 4-nitrophenyl,phenoxyphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-nitroethyl,nitromethyl, and the like. In addition, deuterated substituents R¹ andR² in which at least one hydrogen is replaced with the deuterium isotopemay be employed. Each R¹ is preferably hydrogen or deuterium, and eachR² is preferably an alkyl radical such as methyl, a halogenated alkylradical such as trifluoromethyl, or a deuterated equivalent thereof.

Most often, the chiral indane moieties (IA) and (IB) are derived fromthe enantiomers of 5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-tri(R²)indanes,wherein R² is defined above. Preferably, R² is methyl, and5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl indane, which is alsoreferred to herein as "IBP", is usually used as the starting materialdue to its ease in preparation from commercially available materials.IBP is represented by the following structure: ##STR3## wherein theasterisk (*) represents the chiral carbon. However, it should be notedthat the present invention is not limited to the use of IBP, and othersubstituted indane bisphenols wherein R¹ and R² are defined above areequally effective in producing optically active indane polymersexhibiting the advantageous properties described earlier.

The optical rotational orientations and absolute configurationsassociated with structural moieties (IA) and (IB) derived from theenantiomers of IBP are, respectively, (R)(+) and (S)(-). Thus, as usedherein, "(R)(+)-IBP" refers to(R)(+)-5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl indane and moietiesthereof, and "(S)(-)-IBP" refers to(S)(-)-5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl indane and itsderivatives.

Substituted and unsubstituted racemic indane bisphenols can be preparedaccording to the method disclosed in U.S. Pat. No. 4,334,106 by treatingiso-propenyl phenol (IPP) or a mixture of its linear oligomers with astoichiometric excess of organic acid. IPP can be prepared by basecatalyzed cracking of BPA. The disclosure of U.S. Pat. No. 4,334,106 isincorporated herein by reference. Alternatively, indane bisphenols canbe prepared by reacting the corresponding indanamine with sodium nitritein the presence of aqueous acid as described by J. C. Wilson, Journal ofPolymer Science: Polymer Chemistry Edition 13, 749-754 (1975), which isalso incorporated herein by reference. Also, see U.S. Pat. No.2,979,534, which is also incorporated herein by reference. Theindanamine can be prepared by the method described by J. C. Petropoulosand J. J. Fisher, J. Amer. Chem. Soc. 80, 1938 (1958) from thecorresponding carboxy indane compound, which is also incorporated hereinby reference.

Racemic indane bisphenol mixtures may be resolved into their individualenantiomers for use in the present invention using a lipase-catalyzedstereo- and regio-selective hydrolytic process, which is disclosed forthe preparation of IBP enantiomers in the commonly assigned U.S. patentapplication being filed concurrently herewith and corresponding toAttorney Docket No. 0953.031, the disclosure of which is alsoincorporated herein by reference. Alternatively, the enantiomers may beseparated using traditional separation techniques, such as fractionalcrystallization or HPLC using columns packed with chiral stationaryphase.

The relative amounts of chiral indane structural units (IA), (IB), andof units (II)-(III) and (VI)-(XII) in the polymeric compositions may berepresented as mole fractions, where the mole fraction of (IA) is givenby m, the mole fraction of (IB) is given by n, and the mole fraction ofstructural units (II), (III), (VI), (VII), (VIII), (XI), and (XII) iseach 1-(m+n). In structure (IX), the mole fraction is given by 1-f(m+n),and in structure (X), the mole fraction is represented as 1-f'(m+n),where f and f' each multiply the quantity (m+n) and are each 1 except ifthe sum of m and n is 0.5. Then f and f' may each be 1 or may eachindependently have a value greater than 1 but less than 2. When f and f'are each greater than 1, both formulas (IX) and (X) are selected asstructural units contained in the polymer.

The values of in and n are each independently from 0 to about 1.0, andthe sum of m and n is less than or equal to 1.0. However, the molefractions, m and n, of chiral indane moieties (IA) and (IB) must differ.Otherwise, in polymers containing both enantiomeric moieties, theoptical rotations of structural units (IA) and (IB) would be exactlyequal in magnitude but opposite in direction, and the overall rotationwould have a value of 0. In effect, although the polymer would compriseoptically active monomeric units, (IA) and (IB), the overall opticalactivity would be canceled after polymerization.

Thus, the optically active indane polymers of the present inventioninclude chiral polycarbonate homopolymers containing only structuralunits (IA) or (IB), wherein one of m or n is 1.0, and the other is 0. Inaddition, the invention includes optically active randomcopolycarbonates comprising structural units (IA) and (IB) randomlydispersed throughout the polymer, wherein the sum of m and n is 1.0, andm and n each have numerical values greater than 0. However, as statedabove, the mole fractions of (IA) and (IB), m and n, respectively,cannot be equal in value.

The invention also includes optically active random copolycarbonateswhich comprise optically active indane units (IA) and/or (IB) randomlydistributed in the polymer chain with structural units having formula(II), (III), (VI), (VII), or (VIII). In the random polycarbonates, therelative mole fractions of the structural units contained therein mayvary widely depending on the application and the properties desired. Thesum of m and n is less than 1.0, and the value of one of m or n may be0.

As used herein, the term "random" refers to optically active polymerswherein at least two differing structural units, monomers, or oligomersare randomly dispersed or distributed along the polymeric chainbackbone. An "oligomer" consists of only two, three, four, five, or sixmonomer units (ie. dimer, trimer, tetramer, pentamer, hexamer). A"monomer" is a low molecular weight compound capable of beingpolymerized with itself or other similar compounds and refers also tothe corresponding structural moiety, such as to each of structures (IA),(IB), (II)-(III), or (VI)-(XII), that is contained in the polymericchain.

Alternating chiral polycarbonates, polyurethanes, and polyesters mayalso be prepared, wherein units of (IA) and/or (IB) alternate in thepolymer with structural units selected from (II), (III), (VI), (VII),(VIII), (IX), (X), (XI), or (XII). When one of the mole fractions, m orn, of the chiral indane moiety (IA) or (IB) is about 0.5, and the otherof m and n is 0, then the resulting copolymers are referred to herein as"AB" copolymers. Similar to the AB copolymers, a second type ofalternating copolymer containing both (IA) and (IB) moieties may beprepared in which each unit selected from (II)-(III) or (VI)-(XII)alternates in the chain with a unit of (IA) or a unit of (IB).Otherwise, the placement of each (IA) and (IB) unit in the chain israndom. In this second type of alternating copolymer, both in and n areother than 0, but the sum of m and n is about 0.5. When either structure(IX) or (X) is included in the alternating polymers, then f or f',respectively, is 1. Thus, in the alternating copolymers, the molefraction of the selected formula (II)-(III) or (VI)-(XII) is about 0.5.

In another embodiment, when the sum of m and n is about 0.5, bothformulas (IX) and (X) may be included in the polymer. Such polyesterpolymers are referred to herein as "copolyarylate block polymers". Asused herein, the term "block polymer" refers to a polymer made up ofsections or blocks of one chemical composition and sections or blocks ofa differing chemical composition. Each "block", as used herein, is astructural unit and comprises either an oligomer or a monomer.

In the copolyarylate block polymers, the mole fractions of (IX) and (X)are respectively 1-f(m+n) and 1-f' (m+n), and the values of f and f' areeach independently greater than 1 but less than 2. In one embodiment,one of the mole fractions, m or n, of the chiral indane moieties (IA)and (IB) is about 0.5, and the other of m and n is 0. Alternatively,mole fractions, m and n, are both other than 0, but are not equal invalue. In this case, the sum of m and n is about 0.5, and both moieties(IA) and (IB) are included in the copolyarylate block polymer.

When only chiral structure (IA) having a mole fraction of about 0.5 isincluded in the copolyarylate block polymer, and the mole fraction, n,of (IB) is 0, each respective structural unit of formula (IX) and (X) isconnected to a structural unit of formula (IA) forming a firstcopolyarylate block polymer having structural units or blocks comprisingoligomers (IA-IX) and (IA-X). When only chiral structure (IB) isincluded in the polymer, and the mole fraction, m, of (IA) is 0, eachrespective structural unit of formula (IX) and (X) is connected to astructural unit of formula (IB) to form a second copolyarylate blockpolymer having structural blocks (IB-IX) and (IB-X) ##STR4## In thecopolyarylate block polymers provided above, s is the mole fraction ofstructural oligomeric blocks (IA-IX), 1-s is the mole fraction ofstructural oligomeric blocks (IA-X), t is the mole fraction ofstructural units (IB-IX), and 1-t is the mole fraction of structuralunits (IB-X), and s and t each have a numerical value greater than 0 butless than 1.0. For example, f and f' may each be about 1.5, and s and tmay each be about 0.5. Another example is provided when f is about 1.25,f' is about 1.75, and s and t are each about 0.75. Alternatively, f maybe about 1.75, f' may be about 1.25, and s and t may each be about 0.25.However, the overall mole fraction, m or n, of the chiral indane moiety(IA) or (IB) is about 0.5. In the preferred embodiment, the structuralunits (IA-IX) and (IA-X) in the first copolyarylate block polymer and(IB-IX) and (IB-X) in the second copolyarylate block polymer arerandomly distributed.

The present optically active indane polymers also include polycarbonatepolyester block polymers and polycarbonate polyurethane block polymers.In the present polycarbonate block polymers, as shown in the structuresthat follow, one block comprises an optically active polyester orpolyurethane oligomer, and the second block is a chiral polycarbonatemonomer having structure (IA) or (IB). Briefly, structural units orblocks of (IA-IX), (IA-X), (IA-XI), or (IA-XII) are distributed,typically at random, throughout blocks of (IA) monomers, and blocks of(IB-IX), (IB-X), (IB-XI), or (IB-XII) are distributed throughout therespective (IB) monomers. The overall mole fraction of the chiral indanemoieties (IA) or (IB) in the block polymers is greater than 0.5, andtypically ranges from about 0.60 to about 0.90.

More specifically, in the optically active polycarbonate polyester blockpolymers, one of in and n is greater than about 0.5, and the other of mand n is 0. The polymers include structural units selected from formulas(IX), (X), or (XI). When formula (IX) or (X) is selected, f and f' inthe corresponding mole fractions are 1. When the mole fraction of (IB),n, is 0, the selected structural unit of formula (IX), (X), or (XI) isconnected to a chiral indane structure (IA) forming a first polyesteroligomer having structure (IA-Z). Blocks of the first polyester oligomerand blocks of a first polycarbonate monomer comprising at least onestructural unit (IA) combine to form a first polycarbonate polyesterblock polymer having structural blocks (IA-Z) and (IA) ##STR5## whereinZ represents the selected structural unit (IX), (X), or (XI); u is themole fraction of the first polycarbonate monomer; and 1-u is the molefraction of the first polyester oligomer. The value of u ranges fromabout 0.10 to about 0.90.

When in is 0, each selected structural unit of formula (IX), (X), or(XI) is connected to a structural unit of formula (IB) forming a secondpolyester oligomer having structure (IB-Z). The block polymer comprisesblocks of the second polyester oligomer and blocks of a secondpolycarbonate monomer comprising at least one structural unit (IB). Asecond polycarbonate polyester block polymer is formed having structuralblocks (IB-Z) and (IB) ##STR6## wherein Z is defined above; v is themole fraction of the second polycarbonate monomer; and 1-v is the molefraction of the second polyester oligomer. The value of v ranges fromabout 0.10 to about 0.90. Usually, as stated above, the structuralblocks (IA-Z) and (IA) in the first polycarbonate polyester blockpolymer and (IB-Z) and (IB) in the second polycarbonate polyester blockpolymer are randomly dispersed.

Similarly, optically active polycarbonate polyurethane block polymersmay be prepared. In these polymers, one of m and n is greater than about0.5, the other of m and n is 0, and structural units of formula (XII)are included. When n is 0, each structural unit of formula (XII) isconnected to a structural unit of formula (IA) forming a firstpolyurethane oligomer having structure (IA-XII). The optically activepolymer comprises blocks of the first polyurethane oligomer and blocksof a first polycarbonate monomer comprising at least one structural unit(IA). A first polycarbonate polyurethane block polymer is formedcontaining structural blocks (IA-XII) and (IA) ##STR7## wherein w is themole fraction of the first polycarbonate monomer; 1-w is the molefraction of the first polyurethane oligomer; and w has a numerical valuefrom about 0.10 to about 0.90. Likewise, when m is 0, each structuralunit of formula (XII) is connected to an optically active structuralunit of formula (IB) forming a second polyurethane oligomer havingstructure (IB-XII). The block polymer comprises blocks of the secondpolyurethane oligomer and blocks of a second polycarbonate monomercomprising at least one structural unit (IB). A second polycarbonatepolyurethane block polymer is formed containing structural blocks(IB-XII) and (IB) ##STR8## wherein c is the mole fraction of the secondpolycarbonate monomer; 1-c is the mole fraction of the secondpolyurethane oligomer; and c has a numerical value from about 0.10 toabout 0.90. Typically, the structural blocks (IA-XII) and (IA) in thefirst polycarbonate polyurethane block polymer and (IB-XII) and (IB) inthe second polycarbonate polyurethane block polymer are randomlydistributed.

The relative molar amounts of the structural units contained in theoptically active polymers may also be represented as molar ratios. Thus,in the chiral polycarbonate homopolymers, the molar ratio of structuralunits (IA) or (IB) to structures (II)-(III) or (VI)-(XII) is 100:0. Inthe alternating polycarbonates, polyesters, and polyurethanes, the molarratio of structural units (IA) and/or (IB) to structures (II)-(III) or(VI)-(XII) is 50:50. In the optically active random polycarbonates, themolar ratio of (IA):(IB); of (IA) and (IB)!: (II)-(III) or (VI)-(VIII)!;or of (IA) or (IB)!: (II)-(III) or (VI)-(VIII)! may vary from 99:1 to1:99. However, for the reasons provided above, the molar ratio of(IA):(IB) cannot be 50:50. The molar ratios in the random copolyarylateblock polymers containing units of (IA-IX) and (IA-X) or (IB-IX) and(IB-X) are represented as (IA):(IX):(X) and (IB):(IX):(X), respectively,and have values varying from about 50:1:49 to 50:49:1. The molarproportion of the chiral indane moieties (IA) or (IB) to structures(IX)-(XII) in the homopolycarbonate/polyester andhomopolycarbonate/polyurethane block polymers ranges from about 60:40 toabout 90:10.

The relative molar amounts of the structural moieties contained in thepresent optically active indane polymers can be selected for specificapplications or to enhance certain properties. For example, the opticalrotations are the greatest (highest absolute value) in the polycarbonatehomopolymers and decrease as the amount of chiral indane monomer (IA) or(IB) contained in the polymer decreases. Other properties may be foundto vary with the relative amount of the chiral monomers contained in thepolymers, and one of skill in the art would be able to optimizewhichever property is desirable by adjusting the amount of chiralmonomer appropriately.

The weight average molecular weight (M_(w), kg/mole) of the opticallyactive indane polymers of the present invention may vary widely. Ingeneral, the weight average molecular weight ranges from about 10kg/mole to about 500 kg/mole. A high molecular weight (≧10 kg/mole) isdesirable to ensure that the integrity of the material is maintainedwhen exposed to high temperatures (>150° C.), an important property inhigh temperature processing and optoelectronics applications.

To restate, the optically active polymers of the present inventioninclude a wide variety of novel homopolycarbonates, randomcopolycarbonates, and alternating copolycarbonates, copolyesters, andcopolyurethanes containing chiral indane moieties. In addition, theinvention includes optically active block polyarylate polymers, blockhomopolycarbonate/polyester polymers, and blockhomopolycarbonate/polyurethane polymers. Consideration will now be givento each of these types of optically active indane polymers withpreferred parameters and illustrative methods of preparation.

Unless otherwise indicated, the remaining reactants and reagents used inthe reactions described below are readily available materials. Suchmaterials can be conveniently prepared in accordance with conventionalpreparatory procedures or obtained from commercial sources. Deuteratedcompounds for use in the preparation of deuterated optically activepolymers may be prepared using deuterated reactants in the reactionsbelow.

Use of IBP in the examples that follow are for illustrative purposes,and one of ordinary skill in the art would understand that othersubstituted and unsubstituted indanols may be used instead to providethe optically active polymers of the present invention. The presentinvention is not limited to the specific embodiments found in theexamples.

Polycarbonates

The chiral polycarbonates of the present invention may be formed fromthe polymerization of indanol enantiomers either alone or with variousbisphenols, biphenols, and benzenediols from which structural moieties(II), (III), (VI), (VII) and (VIII) are derived, as discussed below.

Alternating Polycarbonate Copolymers

Procedure 1

The optically active alternating polycarbonate copolymers of the presentinvention, wherein a chiral structural unit of formula (IA) or formula(IB) alternates in the polymeric chain backbone with a structural moietyselected from formulas (II), (III), (VI), (VII) or (VIII), can beconveniently prepared by a conventional condensation polymerizationreaction. In this reaction, an appropriately substituted chiral indanol,such as (R)(+)-IBP or (S)(-)-IBP, or a mixture of indanol enantiomers indiffering molar amounts, is combined with nearly equimolar amounts of anappropriately substituted aromatic bishaloformate compound, such as abischloroformate having formula (XIII) ##STR9## wherein Q is astructural moiety corresponding to one of structures (II), (III), (VI),(VII), or (VIII).

Substituted and unsubstituted bischloroformate compounds may be preparedby the reaction of corresponding aromatic dihydroxy compounds, such asbisphenols, biphenols, or benzenediols, with methylene chloride andphosgene by the method described for BPA by Brunelle et al. in PolymerInt'l 37, 179-186 (1995), which is also incorporated herein byreference.

Aromatic dihydroxy compounds suitable for use in the preparation ofbischloroformates and in the polycarbonate polymerization reactionsdescribed below include racemic indanols from which formula (II) isderived. Racemic IBP, wherein R¹ is hydrogen and R² is methyl may beused. Structural monomer (III), referred to herein as a "spirobiindane"monomer or moiety is generally derived from a racemic6,6'-dihydroxy-3,3,3',3'-tetra(R²) spirobiindane compound, referred toherein as a "spirobiindanol" or "spriobiindane bisphenol". Substitutedand unsubstituted spirobiindane bisphenols for use in the present inventon can be prepared by reacting the appropriately substituted BPA withconcentrated hydrochloric acid, as disclosed by Curtis in J. Chem. Soc.,415-418 (1962), the disclosure of which is incorporated herein byreference. In addition, Baker and Besly, J. Chem. Soc. 1421-24 (1939),U.S. Pat. No. 2,979,534, and Stueben, J. Poly Sci., Part A, 3,3209-17(1965), all of which are incorporated herein by reference,disclose the conversion of bisphenols, such as BPA, to the correspondingspirobiindanols using sulfuric acid, benzenesulfonic acid, orp-toluenesulfonic acid. The preparation of spirobiindanols using theaforementioned condensation reaction of BPA in the presence of sulfuricacid is also described in U.S. Pat. No. 3,271,463, which is alsoincorporated herein by reference. U.S. Pat. No. 4,552,949, which isincorporated herein by reference, discloses the reaction in the presenceof anhydrous methanesulfonic acid or hydrochloric acid, and U.S. Pat.No. 4,605,789, which is also incorporated herein by reference, teachesthe reaction in the presence of strong acid cation exchange resins.

Usually spirobiindane bischloroformate (XIII) containing formula (III)is formed from 6,6'-dihydroxy-3,3,3',3'-tetramethyl spirobiindane (SBI)due to its ease in preparation from BPA. In structural unit (III), eachR is hydrogen, and each R² is methyl when SBI is the spirobiindanol.However, other substituted spirobiindane bisphenol compounds may be usedin the polymerization, wherein R¹ and R² are defined above, and theinvention is not limited to structural moieties derived from SBI.

Aromatic bischloroformates containing structural moiety (VI), wherein xis 0, are prepared from substituted or unsubstituted biphenols. When xis 1, (VI) is a derivative of a substituted or unsubstituted bisphenolwherein a bridging carbon connects the phenol moieties. Due to theircommerciaI availability, structure (VI) is preferably derived from oneof the following: 4,4'-bisphenol, wherein x is 0, and each R¹ ishydrogen; bisphenol A (BPA), wherein x is 1, each R¹ is hydrogen, andeach R² is a methyl group; or 4,4'-(hexafluoroisopropylidene)diphenol,commonly known as hexafluorobisphenol A, wherein x is 1, each R¹ ishydrogen, and each R² is trifluoromethyl.

Benzenediols, from which bischloroformates containing structural units(VII) and (VIII) are formed, include, respectively, hydroquinone andresorcinol, wherein each R¹ is hydrogen. However, substitutedbenzenediols i ay also be used.

Typically, in the polymerization reaction, the molar amount ofbischloroformate (XIII) slightly exceeds that of the chiral indanolcompound(s) in order to produce chloroformate end groups that are latercapped with a monophenol. Initially, in this process, the chiralindanol, such as (R)(+)- or (S)(-)-IBP, or the mixture of the indanolenantiomers, is combined in an inert atmosphere, such as in nitrogen orargon, with 4-N,N-dimethylaminopyridine (DMAP) in methylene chloride.The reaction mixture is heated, and a solution of the aromaticbischloroformate (XIII) in methylene chloride is added over a period ofup to three hours. During the addition, the reaction mixture ismaintained at reflux at a temperature of about 50° C., hen stirred foran additional hour. An excess of 4-cumylphenol is then added and thesolution stirred for an additional hour.

The methylene chloride solution containing the optically activealternating copolycarbonate may then be washed with a 1.0M aqueoussolution of hydrochloric acid, then water and brine. The resultingchiral polymer solution, in CH₂ Cl₂, can then be dried over MgSO₄,followed by concentration using a rotary evaporator. The opticallyactive polycarbonate polymer can be isolated by conventional techniques,such as pouring the solution into vigorously stirred absolute methanol.The optically active alternating copolycarbonate can then be collectedby filtration followed by drying in vacuo.

Procedure 2

Alternatively, the optically active alternating copolycarbonate polymersof the present invention can be prepared by combining nearly equimolaramounts of 1) an appropriately substituted chiral indanebischloroformate compound represented by formula (XIII) above, wherein Qis either structural formula (IA) or (IB), or a mixture of chiral indanebischloroformate enantiomers, wherein each enantiomer is present in amolar amount different from the other; and 2) an appropriatelysubstituted aromatic dihydroxy compound, such as the bisphenols,biphenols, or benzenediols discussed above in connection with thepreparation of bischloroformates (from which structures (II), (III),(VI), (VII), and (VIII) are derived).

Random Polycarbonates

Optically active random indane polycarbonates of the present invention,which comprise structural units (IA) and/or (IB) randomly distributedalong the backbone of the polymeric chain with structural units (II),(III), (VI), (VII), or (VIII), can be conveniently prepared by modifyingthe polymerization method reported by D. J. Brunelle in Macromol. Rep.A28 (Supp. 2), 95-102 (1991), which is incorporated herein by reference.Likewise, random polycarbonates comprising monomers of (IA) and (IB) indiffering molar amounts can also be prepared using the method ofBrunelle.

Briefly, to produce the optically active random copolycarbonate,phosgene or a phosgene equivalent, such as o-nitrophenyl carbonatep-nitrophenyl carbonate (NPC), is added as a transesterification agentto a mixture of a chiral indanol compound, such as (R)(+)-IBP or(S)(-)-IBP; and a bisphenol, biphenol, or benzenediol compound fromwhich structural moieties (II), (III), (VI), (VII), and (VIII) arederived (i.e. those discussed above in connection with the formation ofbischloroformates), in methylene chloride. Alteratively, bothenantiomers of the indanol compound may be reacted alone or incombination with the dihydroxy compounds listed above to produce randomoptically active copolycarbonates containing structural units (IA) and(IB), so long as the molar amounts of the two enantiomers differ.

The amount of phosgene or equivalent thereof added is equimolar to thecombined molar amounts of the aromatic dihydroxy compounds contained inthe mixture (i.e. chiral indane bisphenol(s) and, optionally, racemicindane bisphenol, racemic spirobiindane bisphenol, achiral bisphenol,biphenol, or benzenediol). The process is carried out in an inertatmosphere, such as nitrogen or argon. 4-N,N-Dimethylaminopyridine intoluene is then added to the mixture, while stirring, to catalyze thereaction. The solution is stirred at reflux (˜50° C.) for about 5-10hours, then the heat is removed while the solution continues stirringunder ambient conditions for about 20 additional hours. The randomchiral polycarbonate copolymer can be isolated by conventionaltechniques such as pouring the methylene chloride solution into absolutemethanol while stirring vigorously, followed by filtration and drying invacuo.

Polycarbonate Homopolymers

Similarly, the optically active indane polycarbonate homopolymers of thepresent invention, which comprise recurring units of structure (IA)having a mole fraction, m of 1.0, or recurring units of (IB), wherein nis 1.0, can be prepared using the above method for random copolymers.However, in he homopolymerization reaction, the bisphenol, biphenol, orbenzenediol monomers corresponding to structural moieties (II), (III),(VI), (VII), and (VIII) are omitted from the reaction. During theprocess, an equimolar amount of phosgene or its equivalent is combinedwith the appropriately substituted chiral indanol corresponding to (IA)or (IB).

The following examples are illustrative.

EXAMPLE 1

Alternating Copolycarbonate

In a two-neck round bottomed flask quipped with a stirrer, a refluxcondenser, and an addition funnel, chiral(S)(-)-5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethylindane (670.9 mg,2.50 mmol), 4-N,N-dimethylaminopyridine (DMAP) (623.8 mg, 5.11 mmol),and 10 ml of methylene chloride is stirred under ambient conditions for10-20 minutes. The addition funnel contains a solution of BPAbischloroformate (901.3 mg, 2.55 mmol) in 13 ml CH₂ Cl₂. The system issealed, purged with argon and kept under an atmosphere of argon for theremainder of the reaction. At this time the heat is turned on, andaddition of the chloroformate solution is initiated. The reaction ismaintained at reflux (˜50° C.) while the chloroformate solution is addedover three hours. The reaction is then stirred for one additional hour.4-Cumylphenol (108.2 mg, 0.51 mmol) is added, and the solution isstirred for an additional hour.

The methylene chloride solution containing the polymer is washed with a1.0M aqueous solution of hydrochloric acid, then water and brine. Theresulting polymer solution in methylene chloride is dried over MgSO₄,then concentrated to approximately 20 ml on a rotary evaporator. Thepolymer is isolate pouring this solution into a vigorously stirredvolume of absolute methanol (250 ml). The polymer is collected byfiltration and dried in vacuo for 72 hours. The resulting opticallyactive polycarbonate polymer comprises alternating structural units (IB)derived from (S)(-)-IBP and (VI) derived from BPA, wherein the molefractions of (IB) and (VI) are each 0.50, and wherein each R¹ ishydrogen, each R² is methyl, and x is 1.

EXAMPLE 2

Alternating Copolycarbonate

The procedure of Example 1 is repeated substituting (R)(+)-IBP for(S)(-)-IBP. he resulting optically active copolycarbonate polymercomprises alternating structural units (IA) derived from (R)(+)-IBP and(VI) derived from BPA, wherein the mole fractions of (IA) and (VI) areeach 0.50, and wherein each R¹ is hydrogen, each R² is methyl, and x is1.

EXAMPLE 3

Alternating Copolycarbonate

The procedure of Example 1 is repeated except that 1.75 mmol (469.6 mg)of (S)(-)-IBP and 0.75 mmol (201.3 mg) of (R)(+)-IBP are reacted withthe BPA bischloroformate. The resulting optically active polycarbonatepolymer comprises alternating structural units (IA) or (IB) derived from(S)(-)-IBP and (R)(+)-IBP, respectively, and (VI) derived from BPA,wherein the mole fraction, m, of (IA) is 0.15; the mole fraction, n, of(IB) is 0.35; and the mole fraction of (VI) is 0.50; and wherein each R¹is hydrogen, each R² is methyl, and x is 1.

EXAMPLE 4

Random Copolycarbonate

To produce the random copolycarbonate, BPA (514.2 mg, 2.25 mmol), chiral(S)(-)-IBP (738.1 mg, 2.75 mmol), and o-nitrophenyl carbonate (1.52 g,5.00 mmol) are stirred together in methylene chloride (10 ml) for 10minutes in a two-neck round bottomed flask equipped with a stirrer and areflux condenser. 4-N,N-Dimethylaminopyridine (DMAP) (250 μl of a 0.10Msolution in toluene) is added, and the solution is clarified. Thesolution is stirred at reflux (-50° C.) for 5 hours. The heat is thenremoved, and the solution continues stirring under ambient conditionsfor 20 hours longer.

The polymer is isolated by pouring the methylene chloride solution intoa vigorously stirred volume of absolute methanol (250 ml). Theprecipitated polymer is collected on a Buchner funnel. To remove anylast traces of o-nitrophenol by-product from the polymer, a chloroformsolution containing he polymer is prepared, and the polymer isprecipitated from absolute methanol twice more. The polymer is collectedby filtration and dried in vacuo for 72 hours. The optically activecopolycarbonate polymer comprises structural units (IB) derived from(S)(-)-IBP which are randomly dispersed in the polymeric chain withunits (VI) derived from BPA, wherein each R¹ is hydrogen, each R² ismethyl, and x is 1. The mole fraction, n, of structural units (IB) is0.50, and that of structural units (VI), 1-(m+n), is also 0.50. Thus,the molar proportion, (IB):(VI) (also represented as (S)(-)-IBP:BPA), is5:50.

EXAMPLE 5

Random Copolycarbonate

The procedure of Example 4 is repeated except that 1.75 mmol (469.6 mg)of (S)(-)-IBP and 0.75 mmol (201.3 mg) of (R)(+)-IBP are reacted withthe BPA. The optically active copolycarbonate polymer comprisesstructural units (IB), derived from (S)(-)-IBP, and (IA), derived from(R)(+)-IBP, each unit being randomly dispersed in the polymeric chainwith units (VI) derived from BPA. Each R¹ is hydrogen, and each R² ismethyl. The mole fraction, m, of structural units (IA) is 0.15; the molefraction, n, of (IB) is 0.35; and that of structural units (VI),1-(m+n), is 0.50.

EXAMPLE 6

Random Copolycarbonate

The procedure of Example 4 is repeated substituting an equimolar amountof 6,6'-dihydroxy-3,3,3',3'-tetramethyl spirobiindane (SBI) (771.2 mg,2.50 mmol) for BPA. The optically active copolycarbonate polymercomprises structural units (IB) derived from (S)(-)-IBP, which arerandomly dispersed in the polymeric chain with SBI units (III), whereineach R¹ is hydrogen, and each R² is methyl. The mole fraction, n, ofstructural units (IB) is 0.50, and that of structural units (III),1-(m+n), is also 0.50.

EXAMPLES 7-13

Random Copolycarbonates

The procedure of Example 4 is repeated except that the proportions ofBPA and (S)(-)-IBP are varied to produce several random optically activecopolycarbonates containing structural units IB and VI, wherein each R¹is hydrogen, each R² is methyl, and x is 1. Compositions having thefollowing molar proportions (IA:VI) are prepared: 5:95; 25:75; 50:50;60:40; 65:35; 75:25; and 80:20.

EXAMPLE 14

Random Polycarbonate

The procedure of Example 4 is repeated substituting (S)(-)-IBP (1006.4mg, 3.75 mmol) and (R)(+)-IBP (335.5 mg, 1.25 mmol) for the BPA and(S)(-)-IBP. The optically active copolycarbonate polymer comprisesstructural units (IB) derived from (S)(-)-IBP which are randomlydispersed in the polymeric chain with units (IA) derived from(R)(+)-IBP, wherein each R¹ is hydrogen, and each R² is methyl. The molefraction, m, of structural units (IA) is 0.25, and that of structuralunits (IB), n, is 0.75. Thus, the molar proportion of (S)(-)-IBP to(R)(+)-IBP is 75:25.

EXAMPLE 15

Homopolycarbonate

The procedure of Example 4 is followed except that no BPA is added tothe reaction process. (S)(-)-IBP (1.61 g, 6.0 mmol) ando-nitrophenylcarbonate (1.827 g, 6.01 mmol) in 25 ml methylene chlorideare stirred under an argon atmosphere. A solution of4-N,N-dimethylaminopyridine (DMAP) in toluene (500 μl of a 0.10Msolution) is added, and heat is applied to the flask. The reactionmixture is stirred at reflux (˜55° C.) for 6.5 hours, after which it isstirred at ambient temperature for an additional 17 hours.

The polymer is isolated by precipitating the methylene chloride solutioninto 100 ml of methanol followed by filtering to recover the polymer. Itis precipitated two more times from chloroform into methanol, collected,and dried in vacuo to yield the desired chiral (S)(-)-IBP polycarbonatehomopolymer comprising structural units (IB) derived from (S)(-)-IBP,wherein each R¹ is hydrogen, and each R² is methyl. The mole fraction,n, of structural units (IB) is 1.0.

Polyurethanes

Optically active indane polyurethane polymers, wherein a chiralstructural unit of formula (IA) or (IB) alternates with a structuralunit of formula (XII) may be prepared using a conventional condensationpolymerization process in which a diisocyanate compound shown as (XIV)##STR10## is combined with an equimolar amount of an appropriatelysubstituted chiral indanol, such as (R)(+)-IBP or (S)(-)-IBP, or with anequimolar amount of a mixture of indanol enantiomers, wherein the numberof moles of each enantiomer in the mixture differs. Typically, R² ismethyl, and R¹ is hydrogen in both the indanol and diisocyanatecompounds. An exemplary diisocyanate compound istoluene-2,4-diisocyanate or 2,4-diisocyanato-1-methyl benzene, which iscommercially available from Aldrich as tolylene 2,4-diisocyanate. Theresulting chiral polyurethane polymer includes structural units (XII),wherein R² is methyl and is located on the carbon at position 4 of thephenylene ring. Amide groups are located at the 1 and 3 carbons, and theremaining positions contain hydrogen. Another example usestoluene-2,6-diisocyanate or 2,6-diisocyanato-1-methyl benzene, which iscommercially available from Aldrich as tolylene 2,6-diisocyanate,resulting in a polyurethane wherein a methyl group is located on thecarbon at the 2 position of the phenylene ring of structure (XII); theamide groups are located at carbons 1 and 3; and the remaining carbonsare bonded to hydrogen. However, other substituted and unsubstitutedisocyanate compounds may be used, as will be evident to those of skill.

Typically, the polymerization reaction is conducted in a high boilingpolar aprotic solvent such as dimethyl sulfoxide (DMSO) ortetrahydrofuran (THF). When THF is the solvent, triethylamine may beadded to the mixture while stirring to catalyze the reaction. Processtemperatures are not critical and can vary widely. The polymerizationreactions may be conducted at room temperature, between about 20°-25°C., or alternatively, at elevated temperatures up to about 120° C.

The processes are carried out in an inert atmosphere, such as in argonor nitrogen, over a period of time sufficient to produce the desiredpolymer in adequate yield. Reaction times can vary between about 40minutes and 7 days and are influenced by the reactants, reactanttemperature, the concentration of the reactants (and catalyst ifpresent), the choice of solvent, and other factors known to those ofskill in the art.

The chiral indane polyurethane copolymer can be isolated by conventionaltechniques such as pouring the polymer solution into methanol whilestirring, followed by filtration and drying in vacuo.

The following examples are illustrative.

EXAMPLE 16

In a flask equipped with a stirrer, a condenser and a nitrogen inlet, asolution of tolylene-2,4-diisocyanate (1.74 g, 0.010 mol) in 5 ml methylisobutyl ketone is provided. A solution of(S)(-)-IBP (2.68 g, 0.010 mol)in 5 ml methyl sulfoxide (DMSO) is then added to the flask. The flask isheated to 115° C. and stirred for 2 h. The solution is then stirred for7 days at room temperature. The chiral polymer is isolated by pouringthe solution into 100 ml of vigorously stirred methanol. The powder iscollected on a Buchner funnel and dried under vacuum at 50° C. for 18hours. The resulting optically active polyurethane polymer comprisesalternating structural units (IB) derived from (S)(-)-IBP wherein eachR¹ is hydrogen, and each R² is methyl, and structural units (XII),wherein R² at position 4 is methyl, and R¹ is hydrogen. The molefractions of (IB) and (XII) are each 0.50.

EXAMPLE 17

A dry, 50 ml 2-neck round bottomed flask equipped with a stirrer, acondenser, and a nitrogen inlet is charged with (R)(+)-IBP (1.34 g, 5.00mmol), 5 ml anhydrous tetrahydrofuran (THF) and a catalytic quantity oftriethylamine (50 μl, 0.36 mmol). Tolylene 2,4-diisocyanate (719 μl,5.01 mmol) is added all at once. The solution is stirred under anitrogen atmosphere at 25° C. for 40 minutes. The chiral polymer ispoured into 100 ml of vigorously stirred methanol. The solid iscollected by vacuum filtration and dried in vacuo at 50° C. for 18 h.The resulting optically active polyurethane polymer comprisesalternating structural units (IA), derived from (R)(+)-IBP, andstructural units (XII), wherein the mole fractions of (IA) and (XII) areeach 0.50, and wherein each R¹ is hydrogen, and each R² is methyl. Themethyl group of structural units (XII) is located at the 4 position ofthe phenylene ring, and the amide groups are located at the 1 and 3positions.

Polyesters

The optically active indane polyester polymers in which a chiralstructural unit of formula (IA) or (IB) alternates with a structuralunit of formula (IX), (X), or (XI) may be prepared by conventionalcondensation polymerization reactions. One process combines anappropriately substituted diacid halide, such as a diacid chloridehaving formula (XV) ##STR11## wherein Z is structural moiety (IX), (X),or (XI), with an equimolar amount of an appropriately substituted chiralindanol, such as (R)(+)-IBP or (S)(-)-IBP, or with an equimolar amountof a mixture of indanol enantiomers, wherein the number of moles of eachenantiomer in the mixture differs. The reaction is conducted at roomtemperature in a nonreactive solvent, such as methylene chloride, withthe addition of an acylation catalyst, such as dimethylaminopyridine(DMAP).

Alternatively, an interfacial method for polymerizing the chiralpolyesters may be employed. Using this method, an appropriatelysubstituted diacid halide in a nonreactive solvent, such as anhydrousether or methylene chloride, is added at room temperature to a mixtureof the chiral indanol enantiomer(s), sodium hydroxide, and sodium laurylsulfate in water.

Diacid halides useful in the polymerization may be substituted orunsubstituted and include teraphthaloyl chloride and isophthaloylchloride from which formulas (IX) and (X) are derived, respectively. Theresulting structural moieties are para- or meta-linked with the moietiesof structural units (IA) and/or (IB) forming optically active polyesters(polyarylates). In addition, alkyl dicarboxylic acid halides containingup to 20 carbon atoms, but most often containing 4-8 carbon atoms, maybe used to produce an optically active alkyl polyester polymer havingstructural units (XI), wherein y is the number of carbons in the alkylgroup. For example, adipoyl chloride, succinyl chloride, glutaryldichloride, or pimeloyl chloride may be used.

In addition, by adding equal amounts of substituted or unsubstitutedteraphthaloyl chloride and isophthaloyl chloride to a molar amount ofchiral indanol equal to the sum of the diacid chlorides, an opticallyactive copolyarylate block polymer may be formed in which blockscomprising structure (IA) or (IB) connected with structure (IX) arerandomly distributed in the polymeric chain with blocks comprising thesame selected enantiomeric moiety (IA) or (IB) connected with structure(X). The mole fraction of the (IA) or (IB) moiety is about 0.50, and themole fraction of each of (IX) and (X) is about 0.25. Similarly, byvarying the relative amounts of each acid chloride added to thereaction, copolymers having other percentages of structures (IX) and (X)may also be formed. Also, optically active copolyarylate block polymerscontaining structural moeities (IA), (IB), (IX) and (X), wherein eachchiral moiety is connected to a structure (IX) or (X) and the resultingblocks randomly distributed in the polymeric chain, can be prepared byadding the aforementioned acid chlorides to an equimolar mixture ofindanol enantiomers, provided that the molar amount of each enantiomerin the mixture differs. In these block polymers, the sum of the molefractions of formulas (IA) and (IB) is about 0.5.

The polymerization processes are carried out in an inert atmosphere,such as in argon or nitrogen, over a period of time sufficient toproduce the desired polymer in adequate yield. Reaction times can varybetween about 5 minutes and 4 hours depending on the reactants, theconcentration of the reactants (and catalyst if present), the choice ofsolvent, and other factors known to those of skill in the art. Theoptically active polyester polymers can be isolated by conventionaltechniques such as precipitation in methanol, followed by filtration anddrying in vacuo.

The following examples are illustrative.

EXAMPLE 18

In a two-neck round bottomed flask equipped with a nitrogen inlet,stirrer, a reflux condenser, and an addition funnel filled with asolution of isophthaloyl chloride (IP-Cl, 2.06 g, 0.010 mol) in 25 mlmethylene chloride, chiral (R)(+)-IBP (2.68 g, 0.010 mol) anddimethylaminopyridine (DMAP)(2.57 g, 0.021 mol) in 42 ml methylenechloride are stirred for 10 min. The solution of acid chloride is addedover 60 min. After the monomer addition is complete, the reaction isstirred an additional 3 h at room temperature. The polymer is isolatedby precipitation in 300 ml acetone, followed by collection of the solidby filtration. The solid is taken up in 40 ml chloroform andprecipitated a second tine in 300 ml absolute methanol. The solid isdried in vacuo for 18 h at 60° C. The resulting optically activepolyarylate polymer comprises alternating structural units (IA) derivedfrom (R)(+)-IBP, wherein each R² is methyl and each R¹ is hydrogen, andstructural units (X), wherein each R¹ is hydrogen, and f' is 1. The molefraction, m, of structural units (IA) is 0.50, and the mole fraction of(X) is 0.50.

EXAMPLE 19

The procedure of Example 18 is repeated substituting terephthaloylchloride for isophthaloyl chloride. The resulting polyarylate polymercomprises alternating structural units (IA) derived from (R)(+)-IBP,wherein each R² is methyl and each R¹ is hydrogen, and structural units(IX), wherein each R¹ is hydrogen, and f is 1. The mole fraction, m, ofstructural units (IA) is 0.50, and the mole fraction of (IX) is 0.50.

EXAMPLE 20

The procedure of Example 18 is repeated substituting for the solution ofisophthaloyl chloride a solution containing both isophthaloyl chlorideand terephthaloyl chloride in equimolar amounts (1.03 g, 5 mmol of eachacid chloride) in 25 ml methylene chloride. The resulting polyarylatepolymer comprises structural units (IA)-(X)! randomly dispersed in thepolymeric chain with units (IA)-(IX)!₀₅₀, wherein each of the units hasa mole fraction of 0.50. Structure (IA) is derived from (R)(+)-IBP,wherein each R² is methyl, each R¹ is hydrogen. Each structure offormula (IX), wherein each R¹ is hydrogen, and f is 1.5, is directlyconnected to a structure (IA) to form unit (IA)-(IX)!. Likewise, eachstructure of formula (X), wherein each R¹ is hydrogen, and f' is 1.5, isdirectly connected to a structure (IA) to form unit (IA)-(X)!. The molefraction of each moiety (IX) and (X) is 0.25., and the mole fraction, m,of structural moiety (IA) is 0.50.

EXAMPLE 21

The procedure of Example 18 is repeated substituting for the solution ofisophthaloyl chloride a solution containing isophthaloyl chloride (1.54g, 7.5 mmol) and terephthaloyl chloride (0.515 g, 2.5 mmol) in 25 mlmethylene chloride. The resulting polyarylate polymer comprisesstructural units (IA)-(X)!₀.75, having a mole fraction of 0.75, whichare randomly dispersed in the polymeric chain with units (IA)-(IX)!₀.25having a mole fraction of 0.25. Structure (IA) is derived from(R)(+)-IBP, wherein each R² is methyl, and each R¹ is hydrogen. Eachstructure of formula (IX), wherein each R¹ is hydrogen, and f is 1.25,is directly connected to a structure (IA) to form unit (IA)-(IX)!.Likewise, each structure of formula (X), wherein each R¹ is hydrogen,and f' is 1.75, is directly connected to a structure (IA) to form unit(IA)-(X)!. The mole fraction of moiety (IX) is 0.375, and that of (X) is0.125. The mole fraction, m, of structural moiety (IA) is 0.50.

EXAMPLE 22

Chiral (R) (+)-IBP (2.68 g, 0.010 mol) is stirred in a blender withsodium hydroxide (0.020 mol) and 1-3 mol % sodium lauryl sulfate in 62ml water in a nitrogen atmosphere. A solution of isophthaloyl chloride(2.03 g, 0.010 mol) in 30 ml of a nonreactive solvent, such as anhydrousether or methylene chloride, is added and the mixture is stirred in ablender at low speed for 5 to 10 min. The polymer solution isprecipitated in methanol, and the solid is then dried in vacuo for 18 hat 60° C. The resulting optically active polyarylate polymer comprisesalternating structural units (IA) derived from (R)(+)-IBP, wherein eachR² is methyl and each R¹ is hydrogen, and structural units (X), whereineach R¹ is hydrogen, and f' is 1. The mole fraction, m, of structuralunits (IA) is 0.50, and the mole fraction of (X) is 0.50.

Polycarbonate Polyurethane Block Polymers and Polycarbonate PolyesterBlock Polymers

Optically active block copolymers containing indane chiralhomopolycarbonate monomers and indane chiral polyurethane or polyesteroligomers are also contemplated by the present invention. Theseblock-type polymers can be conveniently prepared by combining theprocesses described above for the synthesis of chiral indanehomopolycarbonates and for the synthesis of chiral indane polyurethanesor polyesters. In this embodiment, the mole fraction of the structuralmoiety (IA) or (IB) is greater than 0.50, and the mole fraction ofstructural moiety (IX), (X), (XI), or (XII) is less than 0.50.Alternatively, in another embodiment, block polymers may be formed bychain extending chiral polycarbonate oligomers formed by the processesdescribed above, with polyurethane or polyester monomers.

In either embodiment, hydroxy-terminated linear chiral polycarbonatemonomers or oligomers replace some or all of the chiral indanol in thereactions described above for the preparation of chiral indanepolyurethanes or polyesters. The hydroxy-terminated polycarbonateoligomers can be prepared by varying the process outlined above for thesynthesis of alternating chiral polycarbonate polymers. An excess ofindane bisphenol is used instead of an excess of bishaloformate. Thus,instead of end-capping the polycarbonate with a monophenol from4-cumylphenol, the polymer is end-capped with a bisphenol.Alternatively, in the processes described above for producing chiralhomopolycarbonates and chiral random copolycarbonates, an excess of thechiral indane bisphenol may be used.

The following examples are illustrative.

EXAMPLE 23

A round bottomed flask fitted with a condenser, addition funnel,nitrogen inlet, and stirrer is charged with (R)(+)-IBP (2.68 g, 0.010mol), dimethylaminopyridine (2.50 g, 0.020 mol), and 35 ml of drymethylene chloride. A solution of the bischloroformate of (R)(+)-IBP(1.97 g, 0.005 mol) and terephthaloyl chloride (1.01 g, 0.005 mol) in 30ml dry methylene chloride is slowly added. After the addition iscomplete, the reaction is heated and stirred at reflux for 1 hour. Thepolymer solution is precipitated in 300 ml methanol. The solid iscollected in a Buchner funnel and dried in vacuo. The resultingoptically active polycarbonate polyarylate polymer comprises moieties(IA), derived from (R)(+)-IBP, and (IX), wherein each R¹ is hydrogen,and each R² is methyl. The mole fraction of randomly dispersedstructural blocks (IA-IX) is 0.50, and the mole fraction of randomstructural blocks (IA) is 0.50. The mole fraction, m, of (IA) is 0.75and the mole fraction of (IX) is 0.25.

EXAMPLE 24

The procedure of Example 1 is repeated except that the molar ratio of(S)(-)-IBP to BPA-bischloroformate is changed. A flask is charged with(S)(-)-IBP (1.34 g, 5.00 mmol), DMAP (1.10 g, 9.00 mmol), and 20 ml (CH₂Cl₂. The reaction mixture is stirred under nitrogen for 20 minutes. Asolution of BPA-bischloroformate (1.413 g, 4.00 mmol) in 20 ml CH₂ Cl₂is added over 5 minutes, and the reaction stirred at reflux for 2 hours.The chiral oligomers having structural blocks (IB-VI) are isolated byprecipitation into methanol.

In a second step, the procedure of Example 17 is followed, except thatthe hydroxy-terminated chiral oligomers from the first step above areused in place of the chiral diol monomer ((R)(+)-IBP). The solid iscollected in a Buchner funnel and dried in vacuo. The resultingoptically active polycarbonate polyurethane polymer comprises structuralblocks (IB-VI), which alternate in the polymeric chain with structuralmoieties (XII). Each R¹ is hydrogen, and each R² is methyl. The molefraction of structural blocks (IB-VI) is 0.50, and the mole fraction ofeach (IB) and (VI) is 0.25. The mole fraction of alternating units (XII)is 0.50.

The optically active indane polymers of the present invention are ofhigh molecular weight making them useful in high temperature processingapplications. In addition, the polymers have high optical rotationsmaking them useful in optoelectronics applications where achiralpolymers cannot be used. Thus, unlike known polycarbonates, polyesters,and polyurethanes, the present optically active indane polymers haveutility in the fabrication of chiral waveguides and can be used aspolarizing coatings, lenses, and/or filters.

While the invention has been particularly shown and described withreference to the preferred embodiments thereof, it will be understood bythose skilled in the art that other changes in form and details may bemade therein without departing from the spirit and scope of theinvention.

We claim:
 1. An optically active linear polymer comprising(a) structuralunits having formula (IA) and formula (IB) ##STR12## and (b) structuralunits selected from the group having formula (II), formula (III),formula (VI), formula (VII), formula (VIII), formula (IX), formula (X),formula (XI), or formula (XII) ##STR13## wherein m is the mole fractionof said structural units (IA) in said polymer, and n is the molefraction of said structural units (IB) in said polymer, m and n eachindependently having a numerical value from 0 to 1.0, wherein thenumerical value of m differs from the numerical value of n, and whereinthe sum of m and n is less than or equal to 1.0; wherein x is 0 or 1; yis 1 to 20; wherein f and f' are each 1 except if the sum of m and n isabout 0.5, then f and f' may each independently have a value greaterthan 1 but less than 2, and both formulas (IX) and (X) are selected asstructural units of part (b); wherein when said structural units of part(b) have formula (IX), (X), (XI), or (XII), then each said structuralunit of part (b) is separated by at least one structural unit of part(a); and wherein each R¹ and each R² is independently hydrogen,deuterium, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkoxyaryl,alkylaryl, arylalkyl, alkoxy, alkoxyalkyl, aryloxyalkyl, haloalkyl,haloaryl, nitro, halogen, cyano, hydroxy, or deuterated equivalentsthereof.
 2. The polymer of claim 1, wherein m or n is 1.0, said polymercomprising structural units of formula (IA) or (IB), respectively. 3.The polymer of claim 1, wherein the sum of m and n is 1.0, m and n eachhave numerical values greater than 0, and said structural units (IA) and(IB) are randomly distributed in said polymer.
 4. The polymer of claim1, wherein the sum of m and n is less than 1.0, said selected structuralunits of part (b) have formula (II), (III), (VI), (VII), or (VIII), andsaid selected strucutural units of parts (a) and (b) are randomlydistributed in said polymer.
 5. The polymer of claim 4, wherein m or nis
 0. 6. The polymer of claim 1, wherein one of m and n is about 0.5,the other of in and n is 0, said structural units of part (b) areselected from formulas (II)-(III) and (VI)-(XII), and f and f' are 1when said selected formula of part (b) is formula (IX) or (X),respectively.
 7. The polymer of claim 6, wherein each said structuralunit of part (a) having a mole fraction of about 0.5 and each saidselected structural unit of part (b) alternate.
 8. The polymer of claim1, wherein m and n are each other than 0, the sum of m and n is about0.5, said structural units of part (b) are selected from formulas(II)-(III) and (VI)-(XII), and f and f' are 1 when said selected formulaof part (b) is formula (IX) or (X), respectively.
 9. The polymer ofclaim 8, wherein each said selected structural unit of part (b)alternates with a structural unit of formula (IA) or formula (IB). 10.The polymer of claim 1, wherein one of m and n is about 0.5, the otherof m and n is 0, and f and f' each independently have a value greaterthan 1 but less than 2, wherein said selected structural units of part(b) comprise formulas (IX) and (X), and wherein each respectivestructural unit of formula (IX) and (X) is connected to a structuralunit of formula (IA) when n is 0 to form to form a first copolyarylateblock polymer having structural blocks (IA-IX) and (IA-X) or to astructural unit of formula (IB) when m is 0 to form a secondcopolyarylate block polymer having structural blocks ##STR14## wherein sis the mole fraction of said structural blocks (IA-IX), 1-s is the molefraction of said structural blocks (IA-X), t is the mole fraction ofsaid structural blocks (IB-IX), and 1-t is the mole fraction of saidstructural blocks (IB-X), wherein s and t each have a numerical valuegreater than 0 but less than 1.0.
 11. The polymer of claim 10, wherein fand f' are each about 1.5, and s and t are each about 0.50.
 12. Thepolymer of claim 10, wherein one of f and f' is about 1.25 and the otherof and f' is about 1.75; s and t are each about 0.75 when f is about1.25 and f' is about 1.75; and s and t are each about 0.25 when f isabout 1.75 and f' is about 1.25.
 13. The polymer of claim 10, whereinsaid structural blocks (IA-IX) and (IA-X) II said first copolyarylateblock polymer are randomly distributed, and said structural blocks(IB-IX) and (IB-X) in said second copolyarylate block polymer arerandomly distributed.
 14. The polymer of claim 1, wherein in and n areeach other than 0, the sum of m and n is about 0.5 and f and f' eachindependently have a value greater than 1 but less than 2, wherein saidselected structural units of part (1)) comprise formulas (IX) and (X),and wherein each respective structural unit of formula (IX) and (X) isconnected to a structural unit of formula (IA) or (IB).
 15. The polymerof claim 1, wherein one of m and n is greater than about 0.5, the otherof m and n is 0, f and f' are 1, and said selected structural units ofpart (b) have formula (IX), (X), or (XI), wherein when n is 0, eachselected structural unit of formula (IX), (X), or (XI) is connected to astructural unit of formula (IA) forming a first polyester oligomerhaving structure (IA-Z), wherein said polymer comprises blocks of saidfirst polyester oligomer and further comprises blocks of a firstpolycarbonate monomer comprising at least one structural unit (IA),wherein a first polycarbonate polyester block polymer is formed havingstructural blocks (IA-Z) and (IA) ##STR15## and wherein when m is 0 eachselected structural unit of formula (IX), (X), or (XI) is connected to astructural unit of formula (IB) forming a second polyester oligomerhaving structure (IB-Z), wherein said polymer comprises blocks of saidsecond polyester oligomer and further comprises blocks of a secondpolycarbonate monomer comprising at least one structural unit (IB),wherein a second polycarbonate polyester block polymer is formed havingstructural blocks (IB-Z) and (IB) ##STR16## wherein Z is selectedstructural unit (IX), (X), or (XI), u is the mole fraction of said firstpolycarbonate monomer, 1-u is the mole fraction of said first polyesteroligomer, v is the mole fraction of said second polycarbonate monomer,1-v is the mole fraction of said second polyester oligomer, wherein uand v each have a numerical value from about 0.10 to about 0.90.
 16. Thepolymer of claim 15, wherein said structural blocks (IA-Z) and (IA) insaid first polycarbonate polyester block polymer are randomlydistributed, and said structural blocks (IB-Z) and (IB) in said secondpolycarbonate polyester block polymer are randomly distributed.
 17. Thepolymer of claim 1, wherein one of m and n is greater than about 0.5,the other of m and n is 0, and said selected structural units of part(b) have formula (XII), wherein when n is 0, each structural unit offormula (XII) is connected to a structural unit of formula (IA) forminga first polyurethane oligomer having structure (IA-XII), wherein saidpolymer comprises blocks of said first polyurethane oligomer and furthercomprises blocks of a first polycarbonate monomer comprising at leastone structural unit (IA), wherein a first polycarbonate polyurethaneblock polymer is formed having structural blocks (IA-XII) and (IA)##STR17## and wherein when m is 0, each structural unit of formula (XII)is connected to a structural unit of formula (IB) forming a secondpolyurethane oligomer having structure (IB-XII), wherein said polymercomprises blocks of said second polyurethane oligomer and furthercomprises blocks of a second polycarbonate monomer comprising at leastone structural unit (IB), wherein a second polycarbonate polyurethaneblock polymer is formed having structural blocks (IB-XII) and (IB)##STR18## wherein w is the mole fraction of said first polycarbonatemonomer, 1-w is the mole fraction of said first polyurethane oligomer, cis the mole fraction of said second polycarbonate monomer, 1-c is themole fraction of said second polyurethane oligomer, and wherein w and ceach have a numerical value from about 0.10 to about 0.90.
 18. Thepolymer of claim 17, wherein said structural blocks (IA-XII) and (IA) insaid first polycarbonate polyurethane block polymer are randomlydistributed, and said structural blocks (IB-XII) and (IB) in said secondpolycarbonate polyurethane block polymer are randomly distributed. 19.The polymer of claim 1, wherein each R¹ is hydrogen or deuterium, andeach R² is methyl, trideuteromethyl, or trifluoromethyl.
 20. The polymerof claim 1, wherein the weight average molecular weight of said polymeris between about 10 kg/mole and 500 kg/mole.
 21. The polymer of claim 1,wherein said formula (IA) is derived from(R)(+)-5-hydroxy-3-(4-hydroxyphenyl)- 1,1,3-trimethyl indane, andwherein said formula (IB) is derived from(S)(-)-5-hydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl indane.